EP0166093B1 - Procédé pour la préparation d'un poly(éther de phénylène) protégé contre la dégradation de son poids molaire - Google Patents

Procédé pour la préparation d'un poly(éther de phénylène) protégé contre la dégradation de son poids molaire Download PDF

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Publication number
EP0166093B1
EP0166093B1 EP85104058A EP85104058A EP0166093B1 EP 0166093 B1 EP0166093 B1 EP 0166093B1 EP 85104058 A EP85104058 A EP 85104058A EP 85104058 A EP85104058 A EP 85104058A EP 0166093 B1 EP0166093 B1 EP 0166093B1
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EP
European Patent Office
Prior art keywords
process according
reaction
sulphide
catalyst
oxygen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP85104058A
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German (de)
English (en)
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EP0166093A1 (fr
Inventor
Martin Dr. Bartmann
Klaus Dr. Burzin
Klaus Dr. Bevers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huels AG
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Huels AG
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Priority to AT85104058T priority Critical patent/ATE28081T1/de
Publication of EP0166093A1 publication Critical patent/EP0166093A1/fr
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Publication of EP0166093B1 publication Critical patent/EP0166093B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying

Definitions

  • the stopping of the polycondensation can, depending on the respective reaction conditions, expediently be carried out either by inactivating the catalyst, by separating the catalyst or by separating the polymer. In individual cases, these measures, in addition to the termination of the polycondensation, bring about an albeit incomplete purification of the polymer.
  • the PPO reaction mixture which contains a copper amine catalyst and the polymer in an aromatic solvent, is stopped and worked up by treatment with CO 2 / water.
  • the separation of the amine from the polymer is unsatisfactory, as Example A shows.
  • DE-OS 15 70 683 describes that 50% sodium hydroxide solution is added to the PPE reaction mixture. This process has not been able to assert itself because it does not reliably terminate the polymerization (cf. DE-OS 24 30 130).
  • a chelating agent can be used to inactivate and separate a copper catalyst (cf. DE-PS 15 70 683, column 15, lines 3 to 5, and DE-OS 26 40 147). Experimental details can also be found in DE-OS 23 64 319.
  • the main disadvantage of all processes that work with chelating agents is the observed degradation of the polymer. It has been found (cf. DE-OS 27 54 887) that the higher the temperature to which they are subjected and the more time that elapses between the end of the reaction and the isolation of the polymer, the faster the polyphenylene ethers are degraded.
  • the viscosity index which is a measure of the average molecular weight of the polymer units, usually decreases by more than 0.1, not infrequently even by 0.2 dl / g, per hour at a temperature of 50 ° C. (DE-OS 27 54 887).
  • DE-PS 15 70 683 mentions that the PPE reaction can also be ended by precipitating the copper as an insoluble compound and filtering it off before the product is isolated.
  • the person skilled in the art may think of a precipitation of the copper salt by introducing H 2 S.
  • there is no precipitation of the copper sulfide which is sparingly soluble.
  • Experiments by the applicant see comparative experiment A) clearly show that copper sulfide does not precipitate at all or only to a very small extent. The reason for the failure to precipitate is unknown.
  • An object of the present invention was to find a process for the preparation of polyphenylene ethers in which the oxidative coupling reaction can be stopped by adding only one agent and the polymer obtained can simultaneously be protected against molecular weight degradation.
  • the process should make it possible to largely free the polymer from catalyst residues and by-products and at the same time to separate the catalyst in a suitable form.
  • the proportions of transition metal and quinone in the polymer should be reduced to values below 5 ppm and 20 ppm, respectively.
  • a polymer of perfect color quality was desired, which can be directly subjected to a direct insulation process.
  • the present invention is based on the knowledge that, under the conditions of the oxidative coupling reaction of di-ortho-substituted phenols, hydrogen sulfide is only suitable as a precipitant for the transition metals used as catalyst components if it is ensured that no oxygen is present.
  • the di-ortho-substituted phenols used are either 2,6-diphenylphenol or 2,6-di-n-alkylphenols, the alkyl radicals of which have 1 to 6 carbon atoms. 2,6-Dimethylphenol is preferred.
  • the catalyst used for the polycondensation is usually a complex of a transition metal, such as copper, cobalt, manganese or nickel, and an organic compound capable of complexing, such as, for. B. amines, especially ethanolamines, ⁇ , ⁇ '-hydroxyarnines, Schiff bases, especially salicylaldehyde derivatives, and oximes.
  • a transition metal such as copper, cobalt, manganese or nickel
  • an organic compound capable of complexing such as, for. B. amines, especially ethanolamines, ⁇ , ⁇ '-hydroxyarnines, Schiff bases, especially salicylaldehyde derivatives, and oximes.
  • the reaction medium can be of very different types (cf. US Pat. No. 3,306,874 and US Pat. No. 3,306,875).
  • a solvent mixture of an aromatic hydrocarbon with 6 to 8 carbon atoms and an aliphatic alcohol with 1 to 4 carbon atoms in a volume ratio of 92.5: 7.5 to 50:50 is preferred, with the restriction that no polyphenylene ether is used during the oxidative coupling reaction should fail.
  • Solvent mixtures of methanol and toluene are particularly preferred.
  • the achievement of a certain degree of polymerization can be determined in various ways.
  • known physical-chemical measurement methods such as that of viscosity determination, can be used to control the degree of polymerization, or simply empirically predefine a specific reaction time.
  • the hydrogen sulfide can be brought into contact with the reaction solution in very different ways.
  • hydrogen sulfide is used in gaseous form.
  • the hydrogen sulfide can be diluted by adding inert gases such as nitrogen, carbon dioxide, hydrogen, carbon monoxide, etc.
  • the gas mixtures should contain at least 2% hydrogen sulfide.
  • a preferred embodiment of the process according to the invention is to bring the reaction solution into contact with the H 2 S-containing gas in cocurrent or countercurrent at 40 to 70 ° C., to separate the precipitated metal sulfide in a solid-liquid separator and then to obtain the polyphenylene ether solution obtained wash with H 2 0, at a volume ratio of organic phase to H 2 0, such as 20: 1 to 1: 2, at 20 to 150 ° C, preferably at 40 to 80 ° C.
  • this washing process can also be carried out under excess pressure.
  • the hydrogen sulfide can then also be brought into contact with the reaction mixture in the form of its preferably aqueous solution.
  • the solutions containing hydrogen sulfide the solutions of soluble metal sulfides, in particular those of the alkali and alkaline earth sulfides, can also be used.
  • Such solutions should contain at least 0.1 mole of sulfide per liter of solution.
  • the sulfide source is used in an amount such that there is preferably 1 to 10 moles, in particular 2 to 5 moles, of sulfide per mole of transition metal compound.
  • the reaction with hydrogen sulfide or the sulfide-containing solutions takes place in the temperature range between 20 and 100 ° C.
  • the desired amount of sulfide-containing solution is first added to the reaction mixture, heated to a temperature between 40 and 70 ° C., the reaction mixture is kept at this temperature for 10 to 20 minutes and then the precipitate formed is centrifuged off.
  • the precipitate obtained is separated off. It is advisable to simply filter it out. However, the separation can also be carried out using a centrifuge, a separator or a decanter.
  • the polycondensation is interrupted at the desired conversion by displacing the oxygen-containing reaction gas, hydrogen sulfide is added and the reaction mixture is brought to the desired temperature. After 1 to 30 minutes, the precipitate formed is removed for. B. by centrifugation.
  • H may be initiated 2 S and brought to the desired temperature when the oxygen content of the footed phase by suitable dosage of the oxygen supply below 6 - 10- 3 Mol / I can be reduced.
  • a continuously operating apparatus such as. B a separator or a full jacket decanter, the metal-containing precipitate can then be separated.
  • the particular advantage of this process is that the metal content of the catalyst, based on concentration values, which are usually between 500 and 5,000 ppm, is reduced in one step to values below 5 ppm and, in addition, the solid metal sulfide obtained is slightly (e.g. B. by roasting and subsequent dissolving in acid) can be converted back into a usable catalyst without the need to work up the otherwise occurring aqueous acidic, alkaline or chelating agents containing stop solutions in a separate step to recover the metal.
  • This reprocessing is necessary to recover the expensive chelating agents and to avoid environmental pollution caused by metal-containing waste water. This applies in particular to copper, which is highly toxic in relation to microorganisms.
  • the J value given in the examples indicates the relative change in viscosity of a 0.5% strength solution of the polymer in chloroform at 25 ° C. in comparison to the pure solvent in accordance with DIN 53 728.
  • the aqueous phase contains 5 ppm Cu.
  • Example 2 As in Example 1, but the H 2 S treatment is carried out at 35 ° C., a mixture of 1,490 g of toluene and 166 g of methanol is used as the solvent, and 170 g of 2,6-diethylphenol are used instead of DMP.
  • Example 1 As in Example 1, but 30 minutes after the end of the DMP addition, the air supply is not switched off, but H 2 S (20 l / h) and air are passed in for 10 minutes. No CuS fails. Refurbishment as example 1.
  • the aqueous phase contains 1,600 ppm Cu.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (11)

1. Procédé de préparation d'un éther polyphénylenique protégé contre une dégradation du poids moléculaire par arrêt de la réaction de copulation oxydante (catalysée par des métaux de transition) de phénols ortho- disubstitués et par séparation des composants métalliques,
caractérisé par le fait
a) que l'on élimine l'oxygène nécessaire pour la réaction de copulation,
b) que l'on met la solution de la réaction seule en contact avec de l'hydrogène sulfuré ou une solution renfermant des ions sulfure, et
c) que l'on sépare le précipité obtenu.
2. Procédé selon la revendication 1, caractérisé par le fait que l'on chasse l'oxygène présent, ou le gaz réactionnel renfermant de l'oxygène, à l'aide d'un gaz inerte, tel que l'azote ou l'argon, par exemple.
3. Procédé selon les revendications 1 et 2, caractérisé par le fait qu'on ajuste la quantité d'oxygène nécessaire pour la réaction oxydante de copulation, de manière telle que lorsque l'on atteint le degré de polymérisation désiré, la quantité globale soit pratiquement consommée.
4. Procédé selon les revendications 1 à 3, caractérisé par le fait qu'à une température de 20 à 100°C, de préférence de 40 à 70°C, on met la solution réactionnelle en contact avec de l'hydrogène sulfuré ou avec une solution renfermant des ions sulfure.
5. Procédé selon les revendications 1 à 4, caractérisé par le fait que le rapport molaire entre le sulfure utilisé et le composé de métal de transition se situe entre 1 : 1 et 10 : 1, de préférence entre 2 : 1 et 5 : 1.
6. Procédé selon les revendications 1 à 5, caractérisé par le fait que l'on utilise comme catalyseur un complexe de cuivre-(11) et une amine.
7. Procédé selon la revendication 6, caractérisé par le fait que le constituant amine du catalyseur est la morpholine.
8. Procédé selon les revendications 1 à 7, caractérisé par le fait qu'on utilise le phénol di-ortho-substitué qu'est le 2,6-diméthyl-phénol.
9. Procédé selon la revendication 6, caractérisé par le fait que l'on utilise comme solvant un mélange d'un hydrocarbure aromatique comportant de 6 à 8 atomes de carbone et d'un alcool aliphatique comportant de 1 à 4 atomes de carbone, dans un rapport volumétrique de 92,5 : 7,5 à 50 : 50.
10. Procédé selon la revendication 9, caractérisé par le fait que l'on utilise un mélange solvant formé de méthanol et de toluène.
11. Procédé selon les revendications 1 à 10, caractérisé par le fait qu'on lave avec de l'eau, à une température de 20 à 150°C, de préférence de 40 à 80°C, la solution d'éther polyphénylénique obtenue après séparation du sulfure metallique.
EP85104058A 1984-05-25 1985-04-03 Procédé pour la préparation d'un poly(éther de phénylène) protégé contre la dégradation de son poids molaire Expired EP0166093B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85104058T ATE28081T1 (de) 1984-05-25 1985-04-03 Verfahren zur herstellung eines gegen molekulargewichtsabbau geschuetzten polyphenylenethers.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843419601 DE3419601A1 (de) 1984-05-25 1984-05-25 Verfahren zur herstellung eines gegen molekulargewichtsabbau geschuetzten polyphenylenethers
DE3419601 1984-05-25

Publications (2)

Publication Number Publication Date
EP0166093A1 EP0166093A1 (fr) 1986-01-02
EP0166093B1 true EP0166093B1 (fr) 1987-07-01

Family

ID=6236884

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EP85104058A Expired EP0166093B1 (fr) 1984-05-25 1985-04-03 Procédé pour la préparation d'un poly(éther de phénylène) protégé contre la dégradation de son poids molaire

Country Status (5)

Country Link
US (1) US4746723A (fr)
EP (1) EP0166093B1 (fr)
JP (1) JPS60258226A (fr)
AT (1) ATE28081T1 (fr)
DE (2) DE3419601A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3910825A1 (de) * 1989-04-04 1990-10-11 Huels Chemische Werke Ag Polyphenylenether-polykondensat-blockcopolymere und verfahren zu ihrer herstellung
JP4765146B2 (ja) * 2000-07-03 2011-09-07 三菱瓦斯化学株式会社 ポリフェニレンエーテルの製造方法
JP4765145B2 (ja) * 2000-07-03 2011-09-07 三菱瓦斯化学株式会社 ポリフェニレンエーテルの製造方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5217559B2 (fr) * 1973-06-26 1977-05-16
US4110311A (en) * 1976-12-13 1978-08-29 General Electric Company Molecular weight control of polyphenylene ethers
US4116939A (en) * 1976-12-20 1978-09-26 General Electric Company Intrinsic viscosity control of polyphenylene ether reaction mixtures
DE3224691A1 (de) * 1982-07-02 1984-01-05 Chemische Werke Hüls AG, 4370 Marl Verfahren zur herstellung von hochmolekularen polyphenylenoxiden
DE3224692A1 (de) * 1982-07-02 1984-01-05 Chemische Werke Hüls AG, 4370 Marl Verfahren zur herstellung von polyphenylenoxiden
DE3234034A1 (de) * 1982-09-14 1984-03-15 Basf Ag, 6700 Ludwigshafen Verfahren zur stabilisierung von polyphenylenetherloesungen
DE3300792A1 (de) * 1983-01-12 1984-07-12 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von bifunktionellen polyphenylenethern
US4463164A (en) * 1983-02-15 1984-07-31 Borg-Warner Chemicals, Inc. Process for preparing polyphenylene ethers

Also Published As

Publication number Publication date
US4746723A (en) 1988-05-24
JPS60258226A (ja) 1985-12-20
DE3560294D1 (en) 1987-08-06
ATE28081T1 (de) 1987-07-15
EP0166093A1 (fr) 1986-01-02
DE3419601A1 (de) 1985-12-05

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